Coated object and process for making the same



June 19, 1945. 4 F. Jv. -soDAY CQATEDOBJECT AND PROCESS FO MAKING THE SAME Filed oct. 1e,.1941

l Patented June 19, `1945 UNITED STATES PATENT OFFICE COATED OBJECT AND PROCESS FOR MAKING THE SAME Frank J. Soday, Swarthmore, Pa., assignor to The United Gas Improvement Company, tion of Pennsylvania Application climber 16, 1941, serial No. 415,221

3 Claims.

This application is a continuation-in-part of my copending application Serial Number 219,557 filed July 16, 1938,.now Patent No. 2,259,497, issued October 21, 1941, Whichpertains generally to the polymerization of unsaturated compounds and pertains particularly to the co-polymerization of such compounds.

The inventionof said copending application. pertains more particularly to co-polymerizing of A manner Aof obtaining soluble catalytically polymerizedcyclopentadiene will be hereinafter described.

There are perhaps Various sources of methyl styrene andl particularly para-methyl styrene. Among these is the light oil obtained upon distillation of tar produced in the manufacture of carburetted Water gas or oil gas. In addition, methyl styrene may be obtained from coal tar,

drip oil, and from cracked petroleum products in general, as well as synthetically.

With ordinary methods of fractional distillation as now practiced, it is impossible to separate the methyl styrene and particularly para-methyl styrene from li'ght oil in a substantially pure state because of the presence of other materials which apparently are either of similar boiling point or are capable of forming azeotropic mixtures with methyl styrene and particularly para-methyl styrene.

For instance, a typical para-methyl styrene fraction obtained by ordinary distillation procsses from light oil will contain hardly more than 50% to 80% para-methyl styrene, and other fractions such as forerunnings and afterrunnings will contain substantially less para-methyl styrene.

Therefore, while pure methyl styrene, and particularly' para-methyl styrene, diluted or not with a solvent, may be employed, the invention is especially useful in that it is also capable of utilizing methyl styrene fractions of various concentrations obtained from other sources such as by distillation vfrom light oil, drip oil, coal tar, cracked petroleum products vin general, and synthetic sources, and including relatively dilute' methyl styrene fractions.

The following examples will serve to further illustrate the invention of said copending application.

Example 1 43.8 grams of a solution of polycyclopentadiene in toluene and containing 7.32 grams of polycyclopentadiene was mixed with 1.16 gramsof a 54.0% solution of para-methyl styrene containing 0.63 gram.of para-methyl styrene. The paramethyl styrene solution was a fraction obtained in the distillation of light oil from carburetted water gas tar.

The mixture was placed in a glass bomb and sealed in an atmosphere of nitrogen.

The bomb was then heated for 4 days at a temperature of 145 C.

44.23 grams of a solution containing 8.62, grams of the desired resin was thus obtained. f

The yield obtained was somewhat above the theoretical which indicates that a portion of the solvent may have reacted and become a part of the resin molecule.

. Example 2 36.2 grams of a solution of polycyclopentadiene in toluene and containing 6.04 grams of polycyclopentadiene was mixed with 8.73 grams of a 54.0% solution of para-methyl styrene containing 4.7 grams of para-methyl styrene. The paramethyl styrene solution was a fraction obtained in'the distillation-of light oil from carburetted water gas tar.

The mixture was placed in a glass bomb and sealed in an atmosphere of nitrogen.

The bomb was then heated for 10 days at temperature of C.

44.13 grams of a solution containing 8.78 grams of the desired resin was thus obtained.

Example 3 of the desired polymer were obtained.

This solution, having a concentration of 11.88% was concentrated in vacuum to approximately A tin coated strip of sheet metal was dipped in the above mentioned solution, air dried for 5,

minutes, and baked for 15 minutes at a temperature of 190 C. A coating of 4.5 milligrams per square inch resulted. This metal strip was then dipped in a solution of Vinylite and -baked for 15 minutes at a temperature of 150 C. A Vinylite coating of 5.68 milligrams per square inchV resulted. The metal-strip was then sterilized 15 minutes in a steam atmosphere with 11-12 pounds-- of steam pressure.

The resulting film was subjected to extremely severe tests for cohesion and adhesion and was found to be very satisfactory.

Example 4 116.8 grams of a solution of polycyclopentadiene in toluene and containing 13.14 grams of polycyclopentadiene were mixed with 2.9 grams of a 53.2% solution of para-methyl styrene containing 1.54 grams of para-methyl styrene. The methyl styrene solution was a fraction obtained in the distillation of light oil from carburetted water gas tar,

The mixture was placed in a glass bomb and sealed in an atmosphere of nitrogen.

The 'bomb was then heated for 10 days at a temperature of 100 C.

119.7 grams of a solution containing 14.22 grams of the desired resin was thus obtained.

While in the above specific examples toluene is used as a polymerization medium, it is to be understood that solvents in general may be employed of which benzene, xylene, ethyl benzene. solvent naphtha, petroleum naphtha, carbon tetrachloride, decalin, triethylbenzene and ethylene dichloride are examples.

Resin compounds prepared as illustrated in the above examples exhibit, among other things, outstanding properties as coating materials.

This invention pertains to the use of my new resinous products in liquid coating compositions, and to the coating of surfaces therewith, for example, surfaces of sheet metal to be made up into food containers such as those commonly known as tin cans.

The term food is employed herein to mean that which is eaten or drunk or absorbed for nourishment or otherwise, and includes not only beverages such as beer, but also substances from which food isprepared, examples of which are coffee beans, whether ground or not, and tea.v

leaves.

It is a well recognized fact that a tin coating for cans is in many instances unsatisfactory, even though the containers are hermetically sealed. In the case of grape juice for instance, tin is dissolved on long standing to degrade the product and should the smallest hole develop in the tin lining a reaction is set up which soon finds its way to the outer surface of the can, thus causing it to leak.

Other food stuffs are known to dissolve or react chemically or to be otherwise affected by the tin lining, for instance modified in taste, or odor and the art has long sought a solution for this difficult problem. y

For example some foods develop hydrogen sulflde on standing. In the case of a. tin coated It is the custom after a can has been sealed to subject it and its contents to a sterilization treatment with heat. This increased temperature greatly accelerates any reactions that are capable of taking place.

The introduction of the sealed can in the beverage trade has increased enormously the demand for a completely inert lining incapable of modifying the taste of the beverage. This applies particularly in the case of beer.

As a result of the foregoing the art has sought to find a lacquer which might be applied over or substituted for the tin coating. It was found, however, that lacquers taken generally either failed to form a suitable bond with the metal surface so as to adhere firmly thereto, or if a proper bond was formed they failed to resist reaction wth foods.

This led to the adoption of a procedure whereby a lacquer. having good bonding properties was used as a primer for a top coat comprising a second lacquer having proper food resisting properties. This in turn presented the further problem of finding two such lacquers which would bond properly with each other. The desired lacquer should, therefore. preferably have universal bonding properties.

Since it is desirable to apply the lacquer coating to the sheet metal before the can or other object or part is made up, the bonding properties of the lacquer must be such as to withstand bending, pressing, shaping, stamping, and so forth, without cracking or losing adhesion.

A common test is to subject a strip of coated sheet metal to considerable stretching during K which the lacquer must not crack or lose adhesion, but must stretch with the metal while adhering firmly thereto.'

Such test may be performed for instance .by coating a tin panel, of any convenient dimensions such as 2 x 3 inches, on one surface with a solution of the resin in a suitable solvent. The quantity applied is conveniently such that the final film after baking will have a weight of from 9 to 11 milligrams per square inch. The temperature of baking is for convenience C. After' baking for one hour and cooling t-he coated tin panel is bent backwardly on itself over a mandrel nl, inch in diameter through an angle of with the coated surface outward. The ends are then bent back into the same pl'ane. The lm must be capable of repeatedly withstanding this manipulation without striation, loss of adhesion,

that withstands this test is perfect from the standpoint of cohesion and adhesion.

In addition to the foregoing the lacquer coating must'also have an acceptable appearance, preferably suggesting utmost cleanliness. This is because the usual housewife looks with great disfavor upon any discoloration of the inside surface of a can when removing food therefrom.

. In thisy connection many lacquers develop a cloudiness during the sterilization step `generally g referred to as blushing. .The resulting discoloration is very undesirable.

Furthermore, the lacquer also should be completely odorless and tasteless in order not to iin` pair the odor or flavor of the'canned food product in any way. I

Surface films having all of the above desirable properties may be produced :by applying to surfaces in general, and metal surfaces such as tin and iron in particular, a liquid coating composition having as a base my'new resin, and then baking or `air drying the coating thus applied, or permitting it to dry in any other atmosphere and/or other manner.

For example, films prepared by applying to tin plate a solution of my new resin in a suitable solvent, for instance, toluene, followed by baking for a period of one hour at 140 C. show excellent coherence and adherence even after repeated bending over a mandrel elf inch in diameter1 and the application of the cross hatching-adhesive tape test.

These films also show excellent alkali and water resistance, do not become brittle with age and are relatively highly resistant to abrasion Examples of the application of my new resin to the coating of surfaces are as follows:

Example 5 of dry resin.

Example 6 A tin plated sheet or other suitable metal sheet or fabricated object is coated with a solution of my new resin in a suitable solvent, say toluene, in suillcient quantities to secure a desired nal coat- `lng weight after drying, say of approximately 5 A suitable coat or series of coats of polymerized vinyl compound may then be applied followed by drying such as by baking, `0r otherwise.

A suitable final coat is of such thickness that thel combined film, that is the lm of my new resin and the film of polymerized vinyl compound, has a total thickness equivalent to from 8 to 1l milligrams per square inch.

Polymerized vinyl compounds are well known inthe art. For instance, a typical polymerized vinyl compound is made by polymerizing a solution containing 85% vinyl chloride and 15% Vinyl acetate on the undiluted basis using benzoyl peroxide as catalyst with mild heat.

This embodiment of my invention is illustrated in Figure 2 of the drawing which represents a somewhat'diagrammatic sectional View of a portion of a tin can." The can end l coated with a primer coat 3 of my new resin and a top coat Since drying is usually hastened by baking, the

coated object after suitable evaporation of solvent is placed in an oven and heated to a suitable temfacture of objects such as cans or" other containers, bo-ttle caps, screwA caps, and in fact objects of any character. It will withstandthe roughest treatment such as sharp bending, stamping, stretching, and so forth without cracking, loosening, or other injury to the coating.

This embodiment of my inventionis illustrated in Figure l of the accompanying drawing which is a somewhat diagrammatic sectional view of va portion of a tin can. The can end l coated with a. dried lm 3 of my new resin is joined by means of the usual can seaming operation to the can side 2 carrying a dried lm 3 of my new resin;

My new liquid coating composition may also be applied to wood, paper, cardboard, nbre board, composition board, asbestos sheets, stoneware, ceramic ware, brick, cement, concrete, etc.

4 of a synthetic resin such as Vinylite is joined by means of the usualv can seaming operation to the can Side 2 coated with a dual film system of` a primer coat 3 of my new resin and a top coat 4 of synthetic resin, such as Vinylite."

While the fllm thicknesses given are found to be suitable for the purpose, and particularly for` food containers, other film thicknesses may obviously be employed without departing from the spirit of the invention.

With respect to the temperature and time of baking, I usually prefer not to exceed about 400.

F. and at such temperatures a baking time not longer than about 15 minutes to avoid any possible injury to the lm. Thus, although my resin films may be safely subjected to higher temperatures during baking, in general, I find temperatures up to 350 F. and baking times up to 30 minutes very satisfactory. With higher temperatures the baking time may be correspondingly shortened l to yield similar satisfactory results.

The use of my new resin is by no means restricted to the formation of a single lm system.

While I refer to baking broadly and to heating in the presence of air or anfoxygen-containing gas as a means of drying my coating or lm, it is to be understood that the taking on of oxygen by the lmneednotnecessarily take place simultaneously with the heating or baking. On the contrary, I may obtain excellent results by heating or baking the coating or the coated ob- 'ject in an inert atmosphere as of nitrogen, carbon dioxide, or the like followed by exposure to the atmosphere or other oxygen-containing medium.

Additional drying or hardening of the lm mayl result from the absorption of oxygen.

Similarly, in preparing my multiple-film systems and particularly a system Vincluding my resin ing or heating in an loxygen-containing atmosphere, or (b) baking my resin lm in an inert atmosphere but permitting it to stand or season" in contact with an oxygen-containing atmosphere for a period of time (for example a week) before applying the top coating of "Vinylite, or (c) baking or heating my resin nlm in an inert atmosphere, coating the baked lm with the top coating of Vinylite and then letting the dual nlm stand or season in contact with an oxygen-containing atmosphere such as before using the coated article for its intended purpose, (inthe last-named case, oxygen may penetrate or seep through the top resin film to my resin primer coat),vor (d) applying and heating my resin nlm in an inert atmosphere, coating with a top coat of another resin film, such as Vinylite, still in an inert atmosphere, and having the multiple-film system thus formed, still in an inert atmosphere, or (e) any combination of any of the foregoing, or otherwise.

My resin films may be satisfactorily hardened either by heat, or by anoxygen-contalning environment or by a combination of both.

In fact, otherA drying or hardening methods may be employed.

As an illustration, my films may be dried or hardened by a vulcanization-like treatment, such as is accomplished by adding a vulcanization agent to the solution at the time of its application, or applying the vulcanization agent over the film after itsapplication, or enclosing thef atmosphere of HzS with the application of heat.

A baking temperature `of 350 F. and a baking time of minutes is illustrative. Y

Vulcanized films may not be oxygen-containing, and may or may not be capable of taking up oxygen, if exposed to the atmosphere or other oxygen-containing gas, say at a greatly reduced rate.

Similar drying procedure may be applied to the vinyl top coat, if desired.

After drying or hardening my films are, generally speaking, insoluble.

While the film thicknesses given are found to be extremely suitable for the purpose, and particularly for food containers, other fllm thicknesses may obviously be employed without departing from the spirit of the invention.

While the foregoing particular description has been concerned primarily with the application of the protective film or films to metal sheets of a gauge used in the manufacture of ,tin cans, it will be obvious that my invention is not limited thereto but may be applied to any metal sheet materiaL and in fact, to metallic objects in general whether pre-fabricated or not, where a tough `strongly adhering nlm or nlm system is desired.

Thus, the resin nlm may be applied to metal u foil.

As an illustration, tin foil and aluminum foil,

' each of which is used to package dairy products rolls. Or a conventional roll type coating procedure may be employed and the solvent removed and/or recovered in a drying tower. l

If desired, metal foil may be strengthened by backing it with paper, or by laminating two or more foil layers. For example, a sheet of metal foil may be coated on one side and the coated side pressed into contact with a. sheet of `paper or second sheet of foil before the coating material has completely dried. This may be followed by coating the opposite side of the metal foil and drying the ilmv for contact with foodstuffs. On the other hand, metal foil coated with my dual lm system with Vinylite as the top coat may be hot pressed against paper or foil to effect union of the materials.

While the invention has been more particularly described in connection with the'coating of sheet metal including foil in the iiat, my resin film or lm system may be applied during or after any forming operations for converting the initial material into the finished object. It is generally .useful for coating metallic objects in general,

whether fabricated from sheet metal or not, or whether pre-fabricated in whole or in part prior to application of the lm or film system.

with my new resin.

poured into molds lined with foil coated in accordance with my invention.

So too, lead foil, such as is used to package tea leaves, may be coated in accordance with my invention.

Metal foil may be vcoated by any desired procedure. For example, the foil may be passed through a solution of the .coating material and the excess removed by means of doctor blades or Eample 7 The China-wood oil* is heated to 350 F. as rapidly as possible, and then heated from 350 F. to 565i' F. during a period of 25 minutes. The bodied linseed oil and the paramethyl styrene- 'polycyclopentadiene resin are added at this point with agitation and the varnish is then chilled to 400 F. The varnish is then reduced by the addition of the mineral spirits.

While any proportion of soluble polycyclcpentadiene to methyl styrene may be employed in making my new resin, I prefer, in the case of coating compositions,v to employ between 50% and 99% soluble polycyclopentadiene lto 1% to 50% monomeric methyl styrene on the undiluted basis. Films made with resins resulting from these proportions are relatively insoluble after drying. 85% to 95% polycyclopentadiene to 5% to 15% monomeric methyl styrene is very suitable 0n the other hand, in the case of casting or molding compositions, I prefer to employ between 50% andl99% monomeric methyl styrene to between 1% to 50% soluble polycyclopentadiene on the undiluted basis. 85% to 95% monomeric methyl -styrene to 5% to 15% soluble polycyclopentadiene is very suitable.

diene to parts of monomeric methyl styrene is excellent'for coating purposes.

The above test for cohesion and adhesion of the applied lm to metal surfaces increases in severity with increase in thickness of the film.

A film on tin plate formed with resin obtained Y upon the polymerization of a solution containing suitable temperature, I nd temperatures between 50 C. and'250 C. satisfactory and prefer to employ temperatures` between 75 C. and 200 C.

iOn the other hand, a catalyst comprising a metallic halide such as tin chloride, zinc chloride, boron trichloride, ferrie chloride,'aluminum chloride, and boron trifiuoride, a metallic halide organic solvent complex, such as AlCla organic solvent complex, aluminum bromide organic solvent co mplex,`zinc chloride organic solvents-complex, boron triuoride organic solvent complex, boron chloride organic solvent complex, or an organic peroxide such as pinene peroxide or benzoyl peroxide, or activated clay, activated carbon, ac-

tivated alumina, silica gel, diatomaceous earth,

ultra Sonics -and/or ultraJ violet light-might be substituted for or combined with heatl for carrying out the polymerization.

I prefer to carry out the polymerization in the presence of an inert gas such as carbon dioxide or nitrogen. or in the presence of solvent vapors 'or in a vacuum to avoid the formation of insoluble gels which are more readily formed in the presence of oxygen. In general, theexclusion of oxygen from the material during and after the polymerizing process will prevent the formation of insoluble compounds.

While I prefer to utilize these resinous materials in the form of solutions because of their pronounced tendency to form insoluble polymers upon exposure to air for any length of time, I wish to point out that the solvent can be removed irom these resins by careful distillation either with or without a reduction in pressure. Such distillation, however, is preferably carried out in an inert atmosphere.

alkyl, alkyl-aryl, alkyl, cycloparaiiinic, cyclooleflnic, hydroaromatic, or naphthenic ring or group.r Included'are secondary amines such as for example Secondary amines containing oneor more aryl A or substituted aryl groups are preferred.

Examples of secondary amines which are particularly satisfactory are diphenyl-p-phenylene diamine, phenyl beta naphthylamine, isopropoxydiphenylamine, aldol alpha naphthylamine (and polymers thereof), symmetrical di beta naphthylpara-phenylenediamine, trimethyl-dihydroquinoline (and polymers thereof), and the ditolylamines. Mixtures of certain of these secondary amines also may be used for this purpose. Included among the mixtures are the commercial products known as Age-Rite Exel, which -is a mixture of isopropoxydiphenylamine and diphenyl-pphenylene diamine, Age-Rite-Hipar,which is a mixture of phenyl beta naphthylamine, isopropoxydiphenylamine, and diphenyl-p-phenylene diamine, and Age-Rite HP, which is a mixture of phenylbeta naptliylamine and diphenyl-pphenylene diamine.

- While .my new resin isv ideally suited tothe coating' of surfaces in general andparticularly to the coating of -m'etal surfaces such as those of' food containers as referredto above, it may be used for many other purposes for instance, for lacquers generally, for varnishes either alone or in admixture with other resins, for enamels, for

paints, or in fact for coating compositions geny erally. It is also well suited for casting and molding purposes, either alone 'or in'admixture The addition of certain anti-oxidants to solutions of the resin/such as'dipentene, pyrogallol,

hydroquinone, p-tertiary butyl catechol and 2-4 diamino phenoldihydrochloride will prevent the formation of insoluble materials apparently indefinitely as Well as improve films prepared from the resins. The mechanism involved is apparently a regulation of the amount of oxygen absorbed by the lm during the drying and baking process.

' Other suitable inhibitors are certain secondary I amines. These secondary amines may be represented by' the following general formula in which R1 is a substituted or unsubstituted aryl, aralkyl, cycloparaiinic, cycloolenic, hyd'roaromatic, or naphthenic ring or group, and in which Risa substituted or an unsubstituted aryl, arylto the reaction mixture followed by agitation for l with other plastics orreslns. Fillers may be added if desired. Suitable llers are wood flour, cotton linters, asbestos, mica, leather nndings, cloth scraps, canvas scraps, clay and the like.

Since my new resin is quick-setting it may have l use as a drier.

A method for producing soluble catalytically polymerized cyclopentadiene is described in the following. example which is taken from my copending application Serial No. 204,786, filed April 2,8, 1,938, now Patent 2,314,904, Vdated March 30, 1943. It is to be understood, however, that Soluble -polycyclopentadiene obtained in anyother way might be substituted.

Example 8 0.30 cubic centimeters of aluminum chloridediethyl ether complex are added to 60 grams of toluene with thorough agitation to form a suspension, emulsionor solution.

A mixture of 20 grams of cyclopentadieneand 20 grams of toluene are added to the suspension during the course of 12 minutes, the temperature ranging-from 2649 C. during the addition. 'I'he mixture is thenagitated for an additional hour, after which 1 cubic centimeter of water is added. This is followed by agitation for 15 minutes.

10 grams of quicklime (CaO) are now added an additional hour. l

5 grams of a suitable lter aid are then added, and the mixture ltered. l

A iiltered solution containing 16.4 grams of polycyclopentadiene is thus obtained.

Generally speaking, -any other aluminum chloride-organic solvent complex might be substichloride complex.'

` stituents of the catalyst by a suitable alkali.

tuted. Examples of these are aluminum chloride-benzene complex, aluminum chloride-tolu-- ene complex, aluminum chloride-pentene complex, aluminum chloride-decene fcomplex, aluminum chloride-phenyl methyl ether complex, aluminum chloride-phenyl ethyl ether complex, aluminum chloride-diisopropyl ether complex, aluminum chloride-isobutene complex, aluminum l vchloride-ethylene complex, aluminum chloridenitrobenzene complex, aluminum chloride-acetone complex, and aluminum chloride-benzoyl In Example 8 it will be noted that both the cyclopentadiene and the catalyst are in diluted form before addition. Furthermore, diluted cyclopentadiene is preferably added to diluted cataylst rather than vice versa to afford a better control of the speed and (uniformity of the reaction and of the amount of heat evolved and consequently the type of polymer produced. The

v reaction runs smoother and is much more easily controlled on a large scale.

' The addition of water to hydrolyze the catalyst makes it possible not only to completely remove the activity of the catalyst and thus stop the reaction. at any point, but also makes it possible to remove the corrosive and discoloring acid con- The alkali is preferably added with the water used -to hydrolyze the catalyst, although it may be added later if desired. The failure .to substantially completely remove the catalyst and its hydrolysis products may be thecause of serious discoloration. The insoluble reaction products formed during the hydrolysis and neutralization remain behind on the llter leaving a highly purined filtrate.

The soluble catalytically polymerized cyclopentadiene may be used as such, or it may be concentrated in a vacuum still of suitable design vto give4 a product containing any desired higherv concentration of polycyclopentadiene including solid polycyclopentadiene, or it might be diluted to give any desired lower concentration, or a .second solvent might be substituted such as a tion of cyclopentadiene, (3) proportion of uniiormly distributed catalyst, and (4) reaction time may be varied considerably in the production of soluble polymer. If it is found that insoluble polymer is obtained, one or more of the four conditions, namely (l) temperature, (2)- concentration of cyclopentadiene (3) proportion of catalyst, and (4) reaction time should be reduced until the soluble polymer is obtained.

Carrying out the polymerization in the presence i oi a solvent makes it possible to have any desired concentration of cyclopentadiene.

While in Example 8 no dilution of the product was required to facilitate hydrolysis and/or nltering. it is to be understood that dilution with a solvent may be employed, if desired, particularly in the case of highly viscous products.

Generally speaking, for the formation of soluble catalytically polymerized cyclopentadiene to the exclusion of insoluble polymer and of extreme discoloration, temperatures should rarely exceed 100 C., and preferably lshould not exceed '70 C., concentrations of cyclopentadiene should rarely exceed 50% by weight of the' total solution except possibly at low temperatures, and concentrations of uniformly distributed catalyst should rarely exceed 25% by weight of cyclopentadiene although these values are not to be considered as fixed limits.v By having extremely low values for one or two of the items mentioned the third might possibly exceed the value given. Should a short reaction time be employed, that is, a reaction time substantially less than one hour, all 'three items might possibly be higher, but perhaps with a sacrice in yieldand color.

It should be kept in mind that there are for practical purposes minimum values for temperature, concentration of cyclopentadiene, proportion of catalyst and time, which practice will show ought t0 be exceeded to obtain reasonable yields. For instance, I iind that when using ordinary commercial tolueneas the solvent at least 1.0 gram of aluminum chloride-ether complex per 100 grams cyclopentadiene is usually required. On thev other hand, if the maximum values given in the previous paragraph for temperature, catalyst and cyclopentadiene were used simultaneously, insoluble polymer would be formed, even though the reaction'time chosen were as short as good practice would permit.

It is by the observance of the preferred principles set forth herein that a quality soluble catalytically pclymerized cyclopentadiene is produced in good yield. v

While in Example 8 toluene is used as a polymerizatlon medium. it is to be understood that any other suitable solvent may be substituted of which benzene, xylene, ethyl benzene, solvent naphtha, petroleum naphtha, carbon tetrachloride, decalin, triethylbenzene and ethylene dichloride are especially suitable. The products with benzene and toluene are preferred for specic uses. Products with tetralin and pentene-Z are also very goed.

While the use of pure cyclopentadiene in solution in a suitable solvent or cyclopentadiene admixed with some methyl cyclopentadiene 'in solution in a suitable solvent simplifies the system from the standpoint of the number of componentspresent, solutions of crude cyclopentadiene in various states of purity might be used with various degrees of success depending upon the results desired.

Examples of crude cyclopentadiene are the cyclopentadiene fractions obtained in the distillation of tar, drip oil and medium and low temperature condensates resulting from subjecting vmanufactured city gas such as carburetted water cyclopentadiene obtained from any other source may be employed without departing from the invention.

Although in the examples given a dilute solution of polycyclopentadiene is used in the preparation of my new resin, it is to be understood that any desired concentration may be employed including highly concentrated solutions as Iwell as solid polycyclopentadiene.

Likewise, monomeric methyl styrene from any other source than light oil-such as drip oil, coal tar,4 cracked petroleum products, and synthetic sources, may be employed without departing from the invention. Buch methyl'styrene may be in any concentration up to and including 100%,

though the polymerization of methyl styrene with polycyclopentadiene is usually 4carried on in the presence of a common solvent which acts as a diluent.

When light oil is the source of methyl styrene an excellent methyl styrene fraction composed more of the ring-substitutedlmethyl styrenes namely ortho, meta and para methyl styrenes'.

For the purpose of convenience in the claims, solubility characteristics will be dened by the term benzene-soluble," though it is to be understood that the actual presence or absence of benzene in the solution or in the applied lms is not implied. f

It is to be understood that the above specifi examples are by way of illustration and that changes, omissions. additions. substitutions, and/or modifications might be made within the scope of the claims without departing from the spirit oi' the invention. v f

I claim:

l. A formed nlm-coated article shaped by deformation of a film-coated metallic body, said formed illm adhering strongly to the formed metal and comprising a primer coat of relatively insoluble dried copolymer of methyl styrene and benzene-soluble l resinous polycyclopentadiene, and a top `coat of a polymerized vinyl compound.

2. A illm coated metal article of which the film coating comprises a primer coat of relatively insoluble dried copolymer of methyl styrene and benzenesoluble resinous polycyclopentadiene. and a top coat of a polymerized vinyl compound.

3. A process for producing a formed metallic article coated with a formed protective layer of synthetic resin which comprises coatingmetaliic sheeting from which the article is to be formed with a copolymer of from 1% to 50% by weight of methyl styrene on the undiluted basis and from article.

l FRANK J. SODA'Y. 

